Refrigerant additive compositions containing perfluoropolyethers

ABSTRACT

The present invention relates to compositions and processes of using perfluoropolyether to maintain or improve the oil return, lubrication, cooling capacity, or energy efficiency of a refrigeration, air conditioning or heat transfer system.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a divisional of and claims priority benefit of U.S.patent application Ser. No. 13/241,540, now U.S. Pat. No. 8,426,657,which is a divisional of and claims priority benefit of U.S. patentapplication Ser. No. 12/796,696, now granted as U.S. Pat. No. 8,049,046,which is a divisional of and claims priority benefit of U.S. patentapplication Ser. No. 11/827,256, now granted as U.S. Pat. No. 7,759,532,which is a continuation-in-part of U.S. patent application Ser. No.11/653,125, filed Jan. 12, 2007, now abandoned, which claims thepriority benefit of U.S. Provisional Application No. 60/758,735, filedJan. 13, 2006.

BACKGROUND OF THE INVENTION

The present invention relates to compositions and processes for use inheat transfer, refrigeration and air-conditioning systems to improve theoil return, lubrication, energy efficiency, or reduce compressor wear,by using perfluoropolyether as an additive in the refrigerant or heattransfer fluid composition.

Lubricants have been used with the fluids in the heat transfer,refrigeration and air-conditioning systems to provide lubrication to thecompressor and other moving parts and reduce compressor wear. However,not all the refrigerants or heat transfer fluids are compatible with allthe lubricants. In particular, many HFC refrigerants or heat transferfluids have poor miscibility or poor dispersibility with commonly usedlubricants, such as mineral oil and alkylbenzene. Because the heattransfer fluids can not readily transport mineral oil lubricants throughthe heat exchangers, the lubricant oils accumulate on the surface of theheat exchange coils, resulting in poor oil return, poor heat exchange,low energy efficiency and the accelerated wear and tear of thecompressors. As a result, the refrigeration and air conditioningindustries have had to resort to the use of more expensive and moredifficult to use synthetic lubricants such as polyolesters andpolyalkylene glycols.

Thus, there is a need for refrigerant additives to improve oil return,lubrication, energy efficiency, or reduce compressor wear while allowingthe use of conventional mineral oil with refrigerants.

BRIEF SUMMARY OF THE INVENTION

The present disclosure provides a composition comprising:

-   -   a) a refrigerant or heat transfer fluid comprising at least one        unsaturated fluorocarbon, selected from the group consisting of:        -   (i) unsaturated fluorocarbons of the formula E- or            Z-R¹CH═CHR², wherein R¹ and R² are, independently, C₁ to C₆            perfluoroalkyl groups;        -   (ii) cyclic unsaturated fluorocarbons of the formula            cyclo-[CX═CY(CZW)_(n)-], wherein X, Y, Z, and W,            independently, are H or F, and n is an integer from 2 to 5;            and        -   (iii) unsaturated fluorocarbons selected from the group            consisting of:            -   1,2,3,3,3-pentafluoro-1-propene (CHF═CFCF₃),                1,1,3,3,3-pentafluoro-1-propene (CF₂═CHCF₃),                1,1,2,3,3-pentafluoro-1-propene (CF₂═CFCHF₂),                1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF₂),                2,3,3,3-tetrafluoro-1-propene (CH₂═CFCF₃),                1,3,3,3-tetrafluoro-1-propeneCHF═CHCF₃),                1,1,2,3-tetrafluoro-1-propene (CF₂═CFCH₂F),                1,1,3,3-tetrafluoro-1-propene (CF₂═CHCHF₂),                1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF₂),                3,3,3-trifluoro-1-propene (CH₂═CHCF₃),                2,3,3-trifluoro-1-propene (CHF₂CF═CH₂);                1,1,2-trifluoro-1-propene (CH₃CF═CF₂);                1,2,3-trifluoro-1-propene (CH₂FCF═CF₂);                1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);                1,3,3-trifluoro-1-propene (CHF₂CH═CHF);                1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);                1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);                1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);                1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);                1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);                1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene                ((CF₃)₂C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene                (CF₂═CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene                (CF₂═CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene                (CF₂═CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene                (CF₃CF₂CF═CH₂); 1,3,3,4,4,4-hexafluoro-1-butene                (CHF═CHCF₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene                (CHF═CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butene                (CHF═CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene                (CHF₂CF═CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene                (CH₂FCF═CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene                (CHF₂CH═CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene                (CF₃CH═CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene                (CF₂═CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene                (CF₂═CFCHFCHF₂);                3,3,3-trifluoro-2-(trifluoromethyl)-1-propene                (CH₂═C(CF₃)₂); 1,1,1,2,4-pentafluoro-2-butene                (CH₂FCH═CFCF₃); 1,1,1,3,4-pentafluoro-2-butene                (CF₃CH═CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene                (CF₃CF₂CH═CH₂); 1,1,1,4,4-pentafluoro-2-butene                (CHF₂CH═CHCF₃); 1,1,1,2,3-pentafluoro-2-butene                (CH₃CF═CFCF₃); 2,3,3,4,4-pentafluoro-1-butene                (CH₂═CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene                (CHF₂CF═CHCHF₂); 1,1,2,3,3-pentafluoro-1-butene                (CH₃CF₂CF═CF₂); 1,1,2,3,4-pentafluoro-2-butene                (CH₂FCF═CFCHF₂);                1,1,3,3,3-pentafluoro-2-methyl-1-propene                (CF₂═C(CF₃)(CH₃));                2-(difluoromethyl)-3,3,3-trifluoro-1-propene                (CH₂═C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene                (CH₂═CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene                (CHF═CFCH₂CF₃); 1,3,4,4,4-pentafluoro-1-butene                (CHF═CHCHFCF₃); 1,3,3,4,4-pentafluoro-1-butene                (CHF═CHCF₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene                (CHF═CFCHFCHF₂); 3,3,4,4-tetrafluoro-1-butene                (CH₂═CHCF₂CHF₂);                1,1-difluoro-2-(difluoromethyl)-1-propene                (CF₂═C(CHF₂)(CH₃));                1,3,3,3-tetrafluoro-2-methyl-1-propene                (CHF═C(CF₃)(CH₃));                3,3-difluoro-2-(difluoromethyl)-1-propene                (CH₂═C(CHF₂)₂); 1,1,1,2-tetrafluoro-2-butene                (CF₃CF═CHCH₃); 1,1,1,3-tetrafluoro-2-butene                (CH₃CF═CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene                (CF₃CF═CFCF₂CF₃);                1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene                (CF₂═CFCF₂CF₂CF₃);                1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene                ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene                (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene                (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene                (CHF═CFCF₂CF₂CF₃);                1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene                (CF₂═CHCF₂CF₂CF₃);                1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene                (CF₂═CFCF₂CF₂CHF₂);                1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene                (CHF₂CF═CFCF₂CF₃);                1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene                (CF₃CF═CFCF₂CHF₂);                1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF₃CF═CFCHFCF₃);                1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene                (CHF═CFCF(CF₃)₂);                1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene                (CF₂═CFCH(CF₃)₂);                1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene                (CF₃CH═C(CF₃)₂);                1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene                (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene                (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene                (CHF═CFCF₂CF₂CHF₂);                3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene                (CH₂═C(CF₃)CF₂CF₃);                1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene                (CF₂═CHCH(CF₃)₂);                1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene                (CHF═CHCF(CF₃)₂);                1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene                (CF₂═C(CF₃)CH₂CF₃);                3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene                ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene                (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene                (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene                (CF₂═CHCF₂CH₂CF₃);                1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene                (CF₃CF═C(CF₃)(CH₃));                2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene                (CH₂═CFCH(CF₃)₂);                1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene                (CHF═CHCH(CF₃)₂);                1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene                (CH₂FCH═C(CF₃)₂);                1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene                (CH₃CF═C(CF₃)₂);                1,1,1-trifluoro-2-(trifluoromethyl)-2-butene                ((CF₃)₂C═CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene                (CF₃CF₂CF═CHCH₃);                1,1,1,4,4,4-hexafluoro-2-methyl-2-butene                (CF₃C(CH₃)═CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene                (CH₂═CHCF₂CHFCF₃);                4,4,4-trifluoro-2-(trifluoromethyl)-1-butene                (CH₂═C(CF₃)CH₂CF₃);                1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene                (CF₃(CF₂)₃CF═CF₂);                1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene                (CF₃CF₂CF═CFCF₂CF₃);                1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene                ((CF₃)₂C═C(CF₃)₂);                1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene                ((CF₃)₂CFCF═CFCF₃);                1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene                ((CF₃)₂C═CHC₂F₅);                1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene                ((CF₃)₂CFCF═CHCF₃);                3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene                (CF₃CF₂CF₂CF₂CH═CH₂);                4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene                (CH₂═CHC(CF₃)₃);                1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene                ((CF₃)₂C═C(CH₃)(CF₃));                2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene                (CH₂═CFCF₂CH(CF₃)₂);                1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene                (CF₃CF═C(CH₃)CF₂CF₃);                1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene                (CF₃CH═CHCH(CF₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene                (CF₃CF₂CF₂CF═CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene                (CH₂═CHCF₂CF₂CF₂CHF₂);                1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene                ((CF₃)₂C═CHCF₂CH₃);                4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene                (CH₂═C(CF₃)CH₂C₂F₅);                3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene                (CF₃CF₂CF₂C(CH₃)═CH₂);                4,4,5,5,6,6,6-heptafluoro-2-hexene (CF₃CF₂CF₂CH═CHCH₃);                4,4,5,5,6,6,6-heptafluoro-1-hexene (CH₂═CHCH₂CF₂C₂F₅);                1,1,1,2,2,3,4-heptafluoro-3-hexene (CF₃CF₂CF═CFC₂H₅);                4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene                (CH₂═CHCH₂CF(CF₃)₂);                1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene                (CF₃CF═CHCH(CF₃)(CH₃));                1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene                ((CF₃)₂C═CFC₂H₅);                1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene                (CF₃CF═CFCF₂CF₂C₂F₅);                1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene                (CF₃CF₂CF═CFCF₂C₂F₅);                1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene                (CF₃CH═CFCF₂CF₂C₂F₅);                1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene                (CF₃CF═CHCF₂CF₂C₂F₅);                1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene                (CF₃CF₂CH═CFCF₂C₂F₅);                1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene                (CF₃CF₂CF═CHCF₂C₂F₅); pentafluoroethyl trifluorovinyl                ether (CF₂═CFOCF₂CF₃); and trifluoromethyl                trifluorovinyl ether (CF₂═CFOCF₃); and    -   b) at least one perfluoropolyether.

DETAILED DESCRIPTION OF THE INVENTION

The refrigerants or heat transfer fluids of the present invention areselected from the group consisting of saturated fluorocarbons,unsaturated fluorocarbons, chlorofluorocarbons,hydrochlorofluorocarbons, fluoroethers, hydrocarbons, carbon dioxide,dimethyl ether, ammonia, iodotrifluoromethane, and combinations thereof.Preferred refrigerants or heat transfer fluids include saturated andunsaturated fluorocarbons and hydrofluorocarbons.

In one embodiment, saturated fluorocarbon refrigerants or heat transferfluids include tetrafluoromethane (PFC-14), hexafluoroethane (PFC-116),octafluoropropane (PFC-218), decafluorobutane (PFC-31-10), fluoromethane(HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23),fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a),1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a),1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2,2-pentafluoroethane(HFC-125), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa),1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea),1,1,1,3,3-pentafluoropropane (HFC-245fa), R-404A (a blend of 44 wt. % ofHFC-125, 52 wt. % of HFC-143a and 4 wt. % of HFC-134a), R-410A (a blendof 50 wt. % of HFC-32 and 50 wt. % of HFC-125), R-417A (a blend of 46.6wt. % of HFC-125, 50 wt. % of HFC-134a and 3.4 wt. % of n-butane),R-422A (a blend of 85.1 wt. % of HFC-125, 11.5 wt. % of HFC-134a, and3.4 wt. % of isobutane), R-407C (a blend of 23 wt. % of HFC-32, 25 wt. %of HFC-125 and 52 wt. % of HFC-134a), R-507A (a blend of 50% R-125 and50% R-143a), and R-508A (a blend of 39% HFC-23 and 61% PFC-116)

In one embodiment, unsaturated fluorocarbon refrigerants and heattransfer fluids comprise compounds with 2 to 12 carbon atoms, in anotherembodiment the unsaturated fluorocarbons comprise compounds with 3 to 10carbon atoms, and in yet another embodiment the unsaturatedfluorocarbons comprise compounds with 3 to 7 carbon atoms.Representative unsaturated fluorocarbons include but are not limited toall compounds as listed in Table 1, Table 2, and Table 3.

The present invention provides unsaturated fluorocarbons having theformula E- or Z-R¹CH═CHR² (Formula I), wherein R¹ and R² are,independently, C₁ to C₆ perfluoroalkyl groups. Examples of R¹ and R²groups include, but are not limited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂,CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃,CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, andC(CF₃)₂CF₂C₂F₅. In one embodiment the unsaturated fluorocarbons ofFormula I, have at least about 4 carbon atoms in the molecule. Inanother embodiment, the unsaturated fluorocarbons of Formula I have atleast about 5 carbon atoms in the molecule. Exemplary, non-limitingFormula I compounds are presented in Table 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2- ene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iECF₃CH═CHCF₂CF—(CF₃)₂1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2- ene F14sECF₃CH═CHCF(CF₃)—C₂F₅1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2- ene F14tECF₃CH═CHC(CF₃)₃ 1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23E C₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-eneF23iE C₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3- ene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-eneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tE CF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex- 2-ene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-eneF24iE C₂F₅CH═CHCF₂CF—(CF₃)₂ 1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene F24sE C₂F₅CH═CHCF(CF₃)—C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5- (trifluoromethyl)hept-3-ene F24tEC₂F₅CH═CHC(CF₃)₃ 1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene F33E C₂F₅CF₂CH═CH—CF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE(CF₃)₂CFCH═CH—CF(CF₃)₂1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex- 3-ene F33iEC₂F₅CF₂CH═CH—CF(CF₃)₂ 1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene F16E CF₃CH═CH(CF₂)₅CF₃1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2- ene F16sECF₃CH═CHCF(CF₃)(CF₂)₂C₂F₅ 1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-ene F16tE CF₃CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2- ene F25EC₂F₅CH═CH(CF₂)₄CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iE C₂F₅CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7- (trifluoromethyl)oct-3-eneF25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅ 1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3-ene F34E C₂F₅CF₂CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4- ene F34iEC₂F₅CF₂CH═CH—CF₂CF(CF₃)₂ 1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-ene F34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6- (trifluoromethyl)oct-4-eneF34tE C₂F₅CF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene F3i4E (CF₃)₂CFCH═CH—(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro- 2(trifluoromethyl)oct-3-eneF3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂ 1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene F3i4sE (CF₃)₂CFCH═CH—CF(CF₃)C₂F₅1,1,1,2,5,6,6,7,7,7-decafluoro-2,5- bis(trifluoromethyl)hept-3-eneF3i4tE (CF₃)₂CFCH═CH—C(CF₃)₃ 1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-ene F26E C₂F₅CH═CH(CF₂)₅CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10- octadecafluorodec-3-ene F26sEC₂F₅CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene F26tE C₂F₅CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5- bis(trifluoromethyl)oct-3-eneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃ 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene F35iE C₂F₅CF₂CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-ene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6- bis(trifluoromethyl)oct-4-eneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene F3i5iE (CF₃)₂CFCH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl)oct-3-eneF3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅ 1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene F44E CF₃(CF₂)₃CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10- octadecafluorodec-5-ene F44iECF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene F44sE CF₃(CF₂)₃CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene F44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,- bis(trifluoromethyl)oct-3-eneF4i4iE (CF₃)₂CFCF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl)oct-4-eneF4i4sE (CF₃)₂CFCF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6- bis(trifluoromethyl)oct-4-eneF4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-ene F4s4sE C₂F₅CF(CF₃)CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6- bis(trifluoromethyl)oct-4-eneF4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃ 1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-ene F4t4tE (CF₃)₃CCH═CH—C(CF₃)₃1,1,1,6,6,6-hexafluoro-2,2,5,5- tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹I with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂.

Said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include fabricated from stainlesssteels, in particular of the austenitic type, and the well-known highnickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickelbased alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may take be conducted in semi-batch mode inwhich the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefinshould be between about 1:1 to about 4:1, preferably from about 1.5:1 to2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1adduct as reported by Jeanneaux, et. al. in Journal of FluorineChemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide withsaid perfluoroalkyltrihydroolefin are preferably within the range ofabout 150° C. to 300° C., preferably from about 170° C. to about 250°C., and most preferably from about 180° C. to about 230° C.

Suitable contact times for the reaction of the perfluoroalkyl iodidewith the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or may preferably be recoveredand purified by distillation prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting thetrihydroiodoperfluoroalkane with a basic substance. Suitable basicsubstances include alkali metal hydroxides (e.g., sodium hydroxide orpotassium hydroxide), alkali metal oxide (for example, sodium oxide),alkaline earth metal hydroxides (e.g., calcium hydroxide), alkalineearth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, ormixtures of basic substances such as soda lime. Preferred basicsubstances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basicsubstance may take place in the liquid phase preferably in the presenceof a solvent capable of dissolving at least a portion of both reactants.Solvents suitable for the dehydroiodination step include one or morepolar organic solvents such as alcohols (e.g., methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol),nitriles (e.g., acetonitrile, propionitrile, butyronitrile,benzonitrile, or adiponitrile), dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choiceof solvent may depend on the boiling point product and the ease ofseparation of traces of the solvent from the product duringpurification. Typically, ethanol or isopropanol are good solvents forthe reaction.

Typically, the dehydroiodination reaction may be carried out by additionof one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction may be fabricated from glass, ceramic, ormetal and is preferably agitated with an impeller or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about10° C. to about 100° C., preferably from about 20° C. to about 70° C.The dehydroiodination reaction may be carried out at ambient pressure orat reduced or elevated pressure. Of note are dehydroiodination reactionsin which the compound of Formula I is distilled out of the reactionvessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted bycontacting an aqueous solution of said basic substance with a solutionof the trihydroiodoperfluoroalkane in one or more organic solvents oflower polarity such as an alkane (e.g., hexane, heptane, or octane),aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g.,methylene chloride, chloroform, carbon tetrachloride, orperchloroethylene), or ether (e.g., diethyl ether, methyl tert-butylether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane,dimethoxyethane, diglyme, or tetraglyme) in the presence of a phasetransfer catalyst. Suitable phase transfer catalysts include quaternaryammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammoniumhydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammoniumchloride, and tricaprylylmethylammonium chloride), quaternaryphosphonium halides (e.g., triphenylmethylphosphonium bromide andtetraphenylphosphonium chloride), or cyclic polyether compounds known inthe art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in theabsence of solvent by adding the trihydroiodoperfluoroalkane to a solidor liquid basic substance.

Suitable reaction times for the dehydroiodination reactions are fromabout 15 minutes to about six hours or more depending on the solubilityof the reactants. Typically the dehydroiodination reaction is rapid andrequires about 30 minutes to about three hours for completion. Thecompound of formula I may be recovered from the dehydroiodinationreaction mixture by phase separation after addition of water, bydistillation, or by a combination thereof.

In another embodiment of the present invention, unsaturatedfluorocarbons comprise cyclic unsaturated fluorocarbons(cyclo-[CX═CY(CZW)_(n)-] (Formula II), wherein X, Y, Z, and W areindependently selected from H and F, and n is an integer from 2 to 5).In one embodiment the unsaturated fluorocarbons of Formula II, have atleast about 3 carbon atoms in the molecule. In another embodiment, theunsaturated fluorocarbons of Formula II have at least about 4 carbonatoms in the molecule. In yet another embodiment, the unsaturatedfluorocarbons of Formula II have at least about 5 carbon atoms in themolecule. Representative cyclic unsaturated fluorocarbons of Formula IIare listed in Table 2.

TABLE 2 Cyclic unsaturated fluorocarbons Structure Chemical nameFC-C1316cc cyclo-CF₂CF₂CF═CF— 1,2,3,3,4,4-hexafluorocyclobuteneHFC-C1334cc cyclo-CF₂CF₂CH═CH— 3,3,4,4-tetrafluorocyclobutene HFC-C1436cyclo-CF₂CF₂CF₂CH═CH— 3,3,4,4,5,5,-hexafluorocyclopentene FC-C1418ycyclo-CF₂CF═CFCF₂CF₂— 1,2,3,3,4,4,5,5- octafluorocyclopenteneFC-C151-10y cyclo-CF₂CF═CFCF₂CF₂CF₂— 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene

The compositions of the present invention may comprise a single compoundof Formula I or formula II, for example, one of the compounds in Table 1or Table 2, or may comprise a combination of compounds of Formula I orformula II.

In another embodiment, unsaturated fluorocarbons may comprise thosecompounds listed in Table 3.

TABLE 3 Name Structure Chemical name HFC-1225ye CF₃CF═CHF1,2,3,3,3-pentafluoro-1-propene HFC-1225zc CF₃CH═CF₂1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF₂CF═CF₂1,1,2,3,3-pentafluoro-1-propene HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF₃CF═CH₂2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF₃CH═CHF1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH₂FCF═CF₂1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF₂CH═CF₂1,1,3,3-tetrafluoro-1-propene HFC-1243yf CHF₂CF═CH₂2,3,3-trifluoro-1-propene HFC-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propeneHFC-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFC-1243zc CH₂FCH═CF₂1,1,3-trifluoro-1-propene HFC-1243ye CH₂FCF═CHF1,2,3-trifluoro-1-propene HFC-1243ze CHF₂CH═CHF1,3,3-trifluoro-1-propene FC-1318my CF₃CF═CFCF₃1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF₃CF₂CF═CF₂1,1,2,3,3,4,4,4-octafluoro-1-butene HFC-1327my CF₃CF═CHCF₃1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF═CFCF₂CF₃1,2,3,3,4,4,4-heptafluoro-1-butene HFC-1327py CHF₂CF═CFCF₃1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF₃)₂C═CHF1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1- propene HFC-1327czCF₂═CHCF₂CF₃ 1,1,3,3,4,4,4-heptafluoro-1-butene HFC-1327cye CF₂═CFCHFCF₃1,1,2,3,4,4,4-heptafluoro-1-butene HFC-1327cyc CF₂═CFCF₂CHF₂1,1,2,3,3,4,4-heptafluoro-1-butene HFC-1336yf CF₃CF₂CF═CH₂2,3,3,4,4,4-hexafluoro-1-butene HFC-1336ze CHF═CHCF₂CF₃1,3,3,4,4,4-hexafluoro-1-butene HFC-1336eye CHF═CFCHFCF₃1,2,3,4,4,4-hexafluoro-1-butene HFC-1336eyc CHF═CFCF₂CHF₂1,2,3,3,4,4-hexafluoro-1-butene HFC-1336pyy CHF₂CF═CFCHF₂1,1,2,3,4,4-hexafluoro-2-butene HFC-1336qy CH₂FCF═CFCF₃1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF₂CH═CFCF₃1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF₃CH═CFCHF₂1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF₂═CFCF₂CH₂F1,1,2,3,3,4-hexafluoro-1-butene HFC-1336pe CF₂═CFCHFCHF₂1,1,2,3,4,4-hexafluoro-1-butene HFC-1336ft CH₂═C(CF₃)₂3,3,3-trifluoro-2-(trifluoromethyl)-1- propene HFC-1345qz CH₂FCH═CFCF₃1,1,1,2,4-pentafluoro-2-butene HFC-1345mzy CF₃CH═CFCH₂F1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF₃CF₂CH═CH₂3,3,4,4,4-pentafluoro-1-butene HFC-1345mzz CHF₂CH═CHCF₃1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH₃CF═CFCF₃1,1,1,2,3-pentafluoro-2-butene HFC-1345fyc CH₂═CFCF₂CHF₂2,3,3,4,4-pentafluoro-1-butene HFC-1345pyz CHF₂CF═CHCHF₂1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH₃CF₂CF═CF₂1,1,2,3,3-pentafluoro-1-butene HFC-1345pyy CH₂FCF═CFCHF₂1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH₂FCF₂CF═CF₂1,2,3,3,4-pentafluoro-1-butene HFC-1345ctm CF₂═C(CF₃)(CH₃)1,1,3,3,3-pentafluoro-2-methyl-1-propene HFC-1345ftp CH₂═C(CHF₂)(CF₃)2-(difluoromethyl)-3,3,3-trifluoro-1- propene HFC1345fye CH₂═CFCHFCF₃2,3,4,4,4-pentafluoro-1-butene HFC-1345eyf CHF═CFCH₂CF₃1,2,4,4,4-pentafluoro-1-butene HFC-1345eze CHF═CHCHFCF₃1,3,4,4,4-pentafluoro-1-butene HFC-1345ezc CHF═CHCF₂CHF₂1,3,3,4,4-pentafluoro-1-butene HFC-1345eye CHF═CFCHFCHF₂1,2,3,4,4-pentafluoro-1-butene HFC-1354fzc CH₂═CHCF₂CHF₂3,3,4,4-tetrafluoro-1-butene HFC-1354ctp CF₂═C(CHF₂)(CH₃)1,1,3,3-tetrafluoro-2-methyl-1-propene HFC-1354etm CHF═C(CF₃)(CH₃)1,3,3,3-tetrafluoro-2-methyl-1-propene HFC-1354tfp CH₂═C(CHF₂)₂2-(difluoromethyl)-3,3-difluoro-1-propene HFC-1354my CF₃CF═CHCH₃1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH₃CF═CHCF₃1,1,1,3-tetrafluoro-2-butene FC-141-10myy CF₃CF═CFCF₂CF₃1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene FC-141-10cy CF₂═CFCF₂CF₂CF₃1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene HFC-1429mzt (CF₃)₂C═CHCF₃1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)- 2-butene HFC-1429myzCF₃CF═CHCF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene HFC-1429mzyCF₃CH═CFCF₂CF₃ 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene HFC-1429eycCHF═CFCF₂CF₂CF₃ 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene HFC-1429czcCF₂═CHCF₂CF₂CF₃ 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene HFC-1429cyccCF₂═CFCF₂CF₂CHF₂ 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene HFC-1429pyyCHF₂CF═CFCF₂CF₃ 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene HFC-1429myycCF₃CF═CFCF₂CHF₂ 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene HFC-1429myyeCF₃CF═CFCHFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene HFC-1429eyymCHF═CFCF(CF₃)₂ 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)- 1-buteneHFC-1429cyzm CF₂═CFCH(CF₃)₂ 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene HFC-1429mzt CF₃CH═C(CF₃)₂1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)- 2-butene HFC-1429czymCF₂═CHCF(CF₃)₂ 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)- 1-buteneHFC-1438fy CH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1-penteneHFC-1438eycc CHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1-penteneHFC-1438ftmc CH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1438czzm CF₂═CHCH(CF₃)₂1,1,4,4,4-pentafluoro-3-(trifluoromethyl)- 1-butene HFC-1438ezymCHF═CHCF(CF₃)₂ 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)- 1-buteneHFC-1438ctmf CF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1447fzy (CF₃)₂CFCH═CH₂3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1- butene HFC-1447fzCF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1-pentene HFC-1447fyccCH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1-pentene HFC-1447czcfCF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1-pentene HFC-1447mytmCF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3-methyl-2- buteneHFC-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFC-1447ezz CHF═CHCH(CF₃)₂1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1- butene HFC-1447qztCH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-2-(trifluoromethyl)-2- buteneHFC-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-butene HFC-1456szt (CF₃)₂C═CHCH₃3-(trifluoromethyl)-4,4,4-trifluoro-2-butene HFC-1456szy CF₃CF₂CF═CHCH₃3,4,4,5,5,5-hexafluoro-2-pentene HFC-1456mstz CF₃C(CH₃)═CHCF₃1,1,1,4,4,4-hexafluoro-2-methyl-2-butene HFC-1456fzce CH₂═CHCF₂CHFCF₃3,3,4,5,5,5-hexafluoro-1-pentene HFC-1456ftmf CH₂═C(CF₃)CH₂CF₃4,4,4-trifluoro-2-(trifluoromethyl)-1-butene FC-151-12c CF₃(CF₂)₃CF═CF₂1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1- hexene (or perfluoro-1-hexene)FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃ 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (or perfluoro-3-hexene) FC-151-12mmtt (CF₃)₂C═C(CF₃)₂1,1,1,4,4,4-hexafluoro-2,3- bis(trifluoromethyl)-2-butene FC-151-12mmzz(CF₃)₂CFCF═CFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene HFC-152- (CF₃)₂C═CHC₂F₅1,1,1,4,4,5,5,5-octafluoro-2- 11mmtz (trifluoromethyl)-2-penteneHFC-152- (CF₃)₂CFCF═CHCF₃ 1,1,1,3,4,5,5,5-octafluoro-4- 11mmyyz(trifluoromethyl)-2-pentene PFBE CF₃CF₂CF₂CF₂CH═CH₂3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (or (or HFC-1549fz)perfluorobutylethylene) HFC-1549fztmm CH₂═CHC(CF₃)₃4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1- butene HFC-1549mmtts(CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene HFC-1549fycz CH₂═CFCF₂CH(CF₃)₂2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)- 1-pentene HFC-1549mytsCF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2- penteneHFC-1549mzzz CF₃CH═CHCH(CF₃)₂1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)- 2-pentene HFC-1558szyCF₃CF₂CF₂CF═CHCH₃ 3,4,4,5,5,6,6,6-octafluoro-2-hexene HFC-1558fzcccCH₂═CHCF₂CF₂CF₂CHF₂ 3,3,4,4,5,5,6,6-octafluoro-2-hexene HFC-1558mmtzc(CF₃)₂C═CHCF₂CH₃ 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)- 2-penteneHFC-1558ftmf CH₂═C(CF₃)CH₂C₂F₅4,4,5,5,5-pentafluoro-2-(trifluoromethyl)- 1-pentene HFC-1567ftsCF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2-methyl-1- penteneHFC-1567szz CF₃CF₂CF₂CH═CHCH₃ 4,4,5,5,6,6,6-heptafluoro-2-hexeneHFC-1567fzfc CH₂═CHCH₂CF₂C₂F₅ 4,4,5,5,6,6,6-heptafluoro-1-hexeneHFC-1567sfyy CF₃CF₂CF═CFC₂H₅ 1,1,1,2,2,3,4-heptafluoro-3-hexeneHFC-1567fzfy CH₂═CHCH₂CF(CF₃)₂4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1- pentene HFC-CF₃CF═CHCH(CF₃)(CH₃) 1,1,1,2,5,5,5-heptafluoro-4-methyl-2- 1567myzzmpentene HFC-1567mmtyf (CF₃)₂C═CFC₂H₅1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2- pentene FC-161-14myyCF₃CF═CFCF₂CF₂C₂F₅ 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene FC-161-14mcyy CF₃CF₂CF═CFCF₂C₂F₅1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene HFC-162-13mzyCF₃CH═CFCF₂CF₂C₂F₅ 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2- hepteneHFC162-13myz CF₃CF═CHCF₂CF₂C₂F₅1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2- heptene HFC-162-CF₃CF₂CH═CFCF₂C₂F₅ 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3- 13mczyheptene HFC-162- CF₃CF₂CF═CHCF₂C₂F₅1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3- 13mcyz heptene PEVECF₂═CFOCF₂CF₃ pentafluoroethyl trifluorovinyl ether PMVE CF₂═CFOCF₃trifluoromethyl trifluorovinyl ether

The compounds listed in Table 2 and Table 3 are available commerciallyor may be prepared by processes known in the art or as described herein.

1,1,1,4,4-pentafluoro-2-butene may be prepared from1,1,1,2,4,4-hexafluorobutane (CHF₂CH₂CHFCF₃) by dehydrofluorination oversolid KOH in the vapor phase at room temperature. The synthesis of1,1,1,2,4,4-hexafluorobutane is described in U.S. Pat. No. 6,066,768,incorporated herein by reference.

1,1,1,4,4,4-hexafluoro-2-butene may be prepared from1,1,1,4,4,4-hexafluoro-2-iodobutane (CF₃CHICH₂CF₃) by reaction with KOHusing a phase transfer catalyst at about 60° C. The synthesis of1,1,1,4,4,4-hexafluoro-2-iodobutane may be carried out by reaction ofperfluoromethyl iodide (CF₃I) and 3,3,3-trifluoropropene (CF₃CH═CH₂) atabout 200° C. under autogenous pressure for about 8 hours.

3,4,4,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorinationof 1,1,1,2,2,3,3-heptafluoropentane (CF₃CF₂CF₂CH₂CH₃) using solid KOH orover a carbon catalyst at 200-300° C. 1,1,1,2,2,3,3-heptafluoropentanemay be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene(CF₃CF₂CF₂CH═CH₂).

1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,3,3,4-heptafluorobutane (CH₂FCF₂CHFCF₃) using solid KOH.

1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,2,4,4-heptafluorobutane (CHF₂CH₂CF₂CF₃) using solid KOH.

1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4,4-heptafluorobutane (CF₃CH₂CF₂CHF₂) using solid KOH.

1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,2,2,3-hexafluorobutane (CH₂FCH₂CF₂CF₃) using solid KOH.

1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4-hexafluorobutane (CF₃CH₂CF₂CH₂F) using solid KOH.

1,1,1,3-tetrafluoro-2-butene may be prepared by reacting1,1,1,3,3-pentafluorobutane (CF₃CH₂CF₂CH₃) with aqueous KOH at 120° C.

1,1,1,4,4,5,5,5-octafluoro-2-pentene may be prepared from(CF₃CHICH₂CF₂CF₃) by reaction with KOH using a phase transfer catalystat about 60° C. The synthesis of4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out by reactionof perfluoroethyliodide (CF₃CF₂I) and 3,3,3-trifluoropropene at about200° C. under autogenous pressure for about 8 hours.

1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF₃CF₂CHICH₂CF₂CF₃) byreaction with KOH using a phase transfer catalyst at about 60° C. Thesynthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane may be carriedout by reaction of perfluoroethyliodide (CF₃CF₂I) and3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂) at about 200° C. underautogenous pressure for about 8 hours.

1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be preparedby the dehydrofluorination of1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane(CF₃CHICH₂CF(CF₃)₂) with KOH in isopropanol. CF₃CHICH₂CF(CF₃)₂ is madefrom reaction of (CF₃)₂CFI with CF₃CH═CH₂ at high temperature, such asabout 200° C.

1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reactionof 1,1,1,4,4,4-hexafluoro-2-butene (CF₃CH═CHCF₃) withtetrafluoroethylene (CF₂═CF₂) and antimony pentafluoride (SbF₅).

2,3,3,4,4-pentafluoro-1-butene may be prepared by dehydrofluorination of1,1,2,2,3,3-hexafluorobutane over fluorided alumina at elevatedtemperature.

2,3,3,4,4,5,5,5-ocatafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solidKOH.

1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane overfluorided alumina at elevated temperature.

Many of the compounds of Formula I, Formula II, Table 1, Table 2, andTable 3 exist as different configurational isomers or stereoisomers.When the specific isomer is not designated, the present invention isintended to include all single configurational isomers, singlestereoisomers, or any combination thereof. For instance, F11E is meantto represent the E-isomer, Z-isomer, or any combination or mixture ofboth isomers in any ratio. As another example, HFC-1225ye is meant torepresent the E-isomer, Z-isomer, or any combination or mixture of bothisomers in any ratio.

Representative chlorofluorocarbon refrigerants or heat transfer fluidsinclude trichlorofluoromethane (CFC-11), dichlorodifluoromethane(CFC-12), 1,1,1-trichlorotrifluoroethane (CFC-113a),1,1,2-trichlorotrifluoroethane (CFC-113), and chloropentafluoroethane(CFC-115).

Representative hydrochlorofluorocarbon refrigerants or heat transferfluids include chlorodifluoromethane (HCFC-22),2-chloro-1,1,1-trifluoroethane (HCFC-123),2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) and1-chloro-1,1-difluoroethane (HCFC-142b).

Representative fluoroether refrigerants or heat transfer fluids includeCF₃OCHF₂, CF₃OCH₃, CF₃OCH₂F, CHF₂OCHF₂, cyclo-(CF₂CF₂CF₂O—), CF₃CF₂OCH₃,CHF₂OCHFCF₃, CHF₂CF₂OCH₃, C₄F₉OCH₃, C₄F₉OC₂H₅, CF₃OCF₃, CF₃OC₂F₅,C₂F₅OC₂F₅ and CF₃OCF(CF₃)CF(CF₃)OCF₃.

Representative hydrocarbon refrigerants or heat transfer fluids includemethane, ethane, propane, cyclopropane, propylene, n-butane,cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane,cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane anddimethylcyclopropane isomers.

In one embodiment, refrigerants or heat transfer fluids may comprisesingle compounds. In another embodiment refrigerants or heat transferfluids may be mixtures of two or more compounds.

In some embodiments, refrigerant or heat transfer fluids may comprise atleast one compound from the group consisting of HFC-1225ye, HFC-1234yf,HFC-1234ze, HFC-1243zf, and mixtures thereof.

In some embodiments, of particular interest are refrigerant and heattransfer fluids comprising at least two compounds selected from thegroup consisting of HFC-1225ye, HFC-1234yf, HFC-32, HFC-125, HFC-134a,and CF₃I.

In another embodiment, refrigerants or heat transfer fluids maycomprise:

-   -   1,2,3,3,3-pentafluoro-1-propene and difluoromethane;    -   1,2,3,3,3-pentafluoro-1-propene, difluoromethane, and        pentafluoroethane;    -   2,3,3,3-tetrafluoro-1-propene and iodotrifluoromethane;    -   1,2,3,3,3-pentafluoro-1-propene, difluoromethane, and        1,1,1,2-tetrafluoroethane;    -   1,2,3,3,3-pentafluoro-1-propene and        2,3,3,3-tetrafluoro-1-propene;    -   1,2,3,3,3-pentafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene,        and difluoromethane;    -   1,2,3,3,3-pentafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene,        and pentafluoroethane;    -   1,2,3,3,3-pentafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene,        and 1,1,1,2-tetrafluoroethane;    -   1,2,3,3,3-pentafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene,        and iodotrifluoromethane;    -   1,2,3,3,3-pentafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene,        difluoromethane, and iodotrifluoromethane;    -   1,2,3,3,3-pentafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene,        and 1,1,1,2-tetrafluoroethane;    -   2,3,3,3-tetrafluoro-1-propene and 1,1,1,2-tetrafluoroethane; or        2,3,3,3-tetrafluoro-1-propene and pentafluoroethane.

In another embodiment, refrigerants or heat transfer fluids maycomprise:

-   -   about 1 weight percent to about 99 weight percent        1,2,3,3,3-pentafluoro-1-propene and about 99 weight percent to        about 1 weight percent difluoromethane, or about 63 weight        percent to about 99 weight percent        1,2,3,3,3-pentafluoro-1-propene and about 37 weight percent to        about 1 weight percent difluoromethane;    -   about 0.1 weight percent to about 98 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 0.1 weight percent to        about 98 weight percent difluoromethane, and about 0.1 weight        percent to about 98 weight percent pentafluoroethane, or about 5        weight percent to about 90 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 5 weight percent to about        90 weight percent difluoromethane, and about 5 weight percent to        about 90 weight percent pentafluoroethane;    -   about 1 weight percent to about 99 weight percent        2,3,3,3-tetrafluoro-1-propene and about 99 weight percent to        about 1 weight percent iodotrifluoromethane, or about 25 weight        percent to about 99 weight percent 2,3,3,3-tetrafluoro-1-propene        and about 75 weight percent to about 1 weight percent        iodotrifluoromethane;    -   about 1 weight percent to about 98 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 1 weight percent to about        98 weight percent difluoromethane, and about 1 weight percent to        about 98 weight percent 1,1,1,2-tetrafluoroethane or about 1        weight percent to about 80 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 1 weight percent to about        80 weight percent difluoromethane, and about 1 weight percent to        about 80 weight percent 1,1,1,2-tetrafluoroethane;    -   about 1 weight percent to about 99 weight percent        1,2,3,3,3-pentafluoro-1-propene and about 99 weight percent to        about 1 weight percent 2,3,3,3-tetrafluoro-1-propene, or about        52 weight percent to about 99 weight percent        1,2,3,3,3-pentafluoro-1-propene and about 48 weight percent to        about 1 weight percent 2,3,3,3-tetrafluoro-1-propene;    -   about 1 weight percent to about 98 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 1 weight percent to about        98 weight percent 2,3,3,3-tetrafluoro-1-propene, and about 0.1        weight percent to about 98 weight percent difluoromethane, or        about 10 weight percent to about 90 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 5 weight percent to about        90 weight percent 2,3,3,3-tetrafluoro-1-propene, and about 0.1        weight percent to about 50 weight percent difluoromethane;    -   about 1 weight percent to about 98 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 1 weight percent to about        98 weight percent 2,3,3,3-tetrafluoro-1-propene, and about 0.1        weight percent to about 98 weight percent pentafluoroethane, or        about 10 weight percent to about 90 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 5 weight percent to about        90 weight percent 2,3,3,3-tetrafluoro-1-propene, and about 0.1        weight percent to about 50 weight percent pentafluoroethane;    -   about 1 weight percent to about 98 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 1 weight percent to about        98 weight percent 2,3,3,3-tetrafluoro-1-propene, and about 0.1        weight percent to about 98 weight percent        1,1,1,2-tetrafluoroethane, or about 10 weight percent to about        90 weight percent 1,2,3,3,3-pentafluoro-1-propene, about 10        weight percent to about 90 weight percent        2,3,3,3-tetrafluoro-1-propene, and about 0.1 weight percent to        about 50 weight percent 1,1,1,2-tetrafluoroethane;    -   about 1 weight percent to about 98 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 1 weight percent to about        98 weight percent 2,3,3,3-tetrafluoro-1-propene, and about 1        weight percent to about 98 weight percent iodotrifluoromethane,        or about 9 weight percent to about 90 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 9 weight percent to about        90 weight percent 2,3,3,3-tetrafluoro-1-propene, and about 1        weight percent to about 60 weight percent iodotrifluoromethane;    -   about 1 weight percent to about 97 weight percent        1,2,3,3,3-pentafluoro-1-propene, about 1 weight percent to about        97 weight percent 2,3,3,3-tetrafluoro-1-propene, about 0.1        weight percent to about 97 weight percent difluoromethane, and        about 1 weight percent to about 97 weight percent        iodotrifluoromethane, or about 10 weight percent to about 80        weight percent 1,2,3,3,3-pentafluoro-1-propene, about 10 weight        percent to about 80 weight percent        2,3,3,3-tetrafluoro-1-propene, about 1 weight percent to about        60 weight percent difluoromethane, and about 1 weight percent to        about 60 weight percent iodotrifluoromethane;    -   about 1 weight percent to about 99 weight percent        2,3,3,3-tetrafluoro-1-propene and about 99 weight percent to        about 1 weight percent 1,1,1,2-tetrafluoroethane, or about 30        weight percent to about 99 weight percent        2,3,3,3-tetrafluoro-1-propene and about 70 weight percent to        about 1 weight percent 1,1,1,2-tetrafluoroethane; or    -   about 0.1 weight percent to about 99.9 weight percent        2,3,3,3-tetrafluoro-1-propene and about 99.9 weight percent to        about 0.1 weight percent pentafluoroethane.

The present invention provides perfluoropolyethers as additives whichare miscible with chlorofluorocarbon and hydrofluorocarbon refrigerantsor heat transfer fluids. A common characteristic of perfluoropolyethersis the presence of perfluoroalkyl ether moieties. Perfluoropolyether issynonymous to perfluoropolyalkylether. Other synonymous terms frequentlyused include “PFPE”, “PFAE”, “PFPE oil”, “PFPE fluid”, and “PFPAE”. Forexample, Krytox®, available from DuPont, is a perfluoropolyether havingthe formula of CF₃—(CF₂)₂—O—[CF(CF₃)—CF₂—O]j′-R′f. In the formula, j′ is2-100, inclusive and R′f is CF₂CF₃, a C3 to C6 perfluoroalkyl group, orcombinations thereof.

Other PFPEs including the Fomblin® and Galden® fluids, available fromAusimont, Milan, Italy and produced by perfluoroolefin photo oxidation,can also be used. Fomblin®-Y can have the formula ofCF₃O(CF₂CF(CF₃)—O—)_(m)′(CF₂—O—)_(n)—R_(1f). Also suitable isCF₃O[CF₂CF(CF₃)O]_(m′)(CF₂CF₂O)_(o), (CF₂O)_(n)—R_(1f). In the formulaeR_(1f) is CF₃, C₂F₅, C₃F₇, or combinations of two or more thereof;(m′+n′) is 8-45, inclusive; and m/n is 20-1000, inclusive; o′ is 1;(m′+n′+o′) is 8-45, inclusive; m′/n′ is 20-1000, inclusive.

Fomblin®-Z can have the formula of CF₃O(CF₂CF₂—O)_(p), (CF₂—O)_(q), CF₃where (p′+q′) is 40-180 and p′/q′ is 0.5-2, inclusive.

Demnum™ fluids, another family of PFPE available from Daikin Industries,Japan, can also be used. It can be produced by sequentialoligomerization and fluorination of 2,2,3,3-tetrafluorooxetane, yieldingthe formula of F—[(CF₂)₃—O]_(t′)—R_(2f) where R_(2f) is CF₃, C₂F₅, orcombinations thereof and t′ is 2-200, inclusive.

The two end groups of the perfluoropolyether, independently, can befunctionalized or unfunctionalized. In an unfunctionalizedperfluoropolyether, the end group can be branched or straight chainperfluoroalkyl radical end groups. Examples of such perfluoropolyetherscan have the formula of C_(r′)F_((2r+1))-A-C_(r′)F_((2r+1)) in whicheach r′ is independently 3 to 6; A can be O—(CF(CF₃)CF₂—O)_(w′),O(CF₂—O)_(x′)(CF₂CF₂—O)_(y′), O—(C₂F₄—O)_(w′),O—(C₂F₄—O)_(x′)(C₃F₆—O)_(y′), O—(CF(CF₃)CF₂—O)_(x′)(CF₂O)_(y′),O—(CF₂CF₂CF₂—O)_(w′),—O—(CF(CF₃)CF₂—O)_(x′)(CF₂CF₂—O)_(y′)-(CF₂—O)_(z′), or combinations oftwo or more thereof; preferably A is O—(CF(CF₃)CF₂—O)_(w′),O—(C₂F₄—O)_(w′), O—(C₂F₄—O)_(x′), (C₃F₆—O)_(y′), O—(CF₂CF₂CF₂—O)_(w′) orcombinations of two or more thereof; w′ is 4 to 100; x′ and y′ are eachindependently 1 to 100. Specific examples include, but are not limitedto, F(CF(CF₃)—CF₂—O)₉—CF₂CF₃, F(CF(CF₃)—CF₂—O)₉—CF(CF₃)₂, andcombinations thereof. In such PFPEs, up to 30% of the halogen atoms canbe halogens other than fluorine, such as, for example, chlorine atoms.

The two end groups of the perfluoropolyether, independently, can also befunctionalized. A typical functionalized end group can be selected fromthe group consisting of esters, hydroxyls, amines, amides, cyanos,carboxylic acids and sulfonic acids

Representative ester end groups include —COOCH₃, —COOCH₂CH₃, —CF₂COOCH₃,—CF₂COOCH₂CH₃, —CF₂CF₂COOCH₃, —CF₂CF₂COOCH₂CH₃, —CF₂CH₂COOCH₃,—CF₂CF₂CH₂COOCH₃, —CF₂CH₂CH₂COOCH₃, —CF₂CF₂CH₂CH₂COOCH₃.

Representative hydroxyl end groups include —CF₂OH, —CF₂CF₂OH, —CF₂CH₂OH,—CF₂CF₂CH₂OH, —CF₂CH₂CH₂OH, —CF₂CF₂CH₂CH₂OH.

Representative amine end groups include —CF₂NR¹R², —CF₂CF₂NR¹R²,—CF₂CH₂NR¹R², —CF₂CF₂CH₂NR¹R², —CF₂CH₂CH₂NR¹R², —CF₂CF₂CH₂CH₂NR¹R²,wherein R¹ and R² are independently H, CH₃, or CH₂CH₃.

Representative amide end groups include —CF₂C(O)NR¹R², —CF₂CF₂C(O)NR¹R²,—CF₂CH₂C(O)NR¹R², —CF₂CF₂CH₂C(O)NR¹R², —CF₂CH₂CH₂C(O)NR¹R²,—CF₂CF₂CH₂CH₂C(O)NR¹R², wherein R¹ and R² are independently H, CH₃, orCH₂CH₃.

Representative cyano end groups include —CF₂CN, —CF₂CF₂CN, —CF₂CH₂CN,—CF₂CF₂CH₂CN, —CF₂CH₂CH₂CN, —CF₂CF₂CH₂CH₂CN.

Representative carboxylic acid end groups include —CF₂COOH, —CF₂CF₂COOH,—CF₂CH₂COOH, —CF₂CF₂CH₂COOH, —CF₂CH₂CH₂COOH, —CF₂CF₂CH₂CH₂COOH.

Representative sulfonic acid end groups include —S(O)(O)OR³, —S(O)(O)R⁴,—CF₂OS(O)(O)OR³, —CF₂CF₂OS(O)(O)OR³, —CF₂CH₂OS(O)(O)OR³,—CF₂CF₂CH₂OS(O)(O)OR³, —CF₂CH₂CH₂OS(O)(O)OR³, —CF₂CF₂CH₂CH₂OS(O)(O)OR³,—CF₂S(O)(O)OR³, —CF₂CF₂S(O)(O)OR³, —CF₂CH₂S(O)(O)OR³,—CF₂CF₂CH₂S(O)(O)OR³, —CF₂CH₂CH₂S(O)(O)OR³, —CF₂CF₂CH₂CH₂S(O)(O)OR³,—CF₂OS(O)(O)R⁴, —CF₂CF₂OS(O)(O)R⁴, —CF₂CH₂OS(O)(O)R⁴,—CF₂CF₂CH₂OS(O)(O)R⁴, —CF₂CH₂CH₂OS(O)(O)R⁴, —CF₂CF₂CH₂CH₂OS(O)(O)R⁴,wherein R³ is H, CH₃, CH₂CH₃, CH₂CF₃, CF₃, or CF₂CF₃, R⁴ is CH₃, CH₂CH₃,CH₂CF₃, CF₃, or CF₂CF₃.

The refrigerant-perfluoropolyether additive combination of thisinvention improves performance of refrigeration, air conditioning andheat transfer system in one or more aspects. In one aspect, it enablesadequate oil return to the compressor such that oil levels aremaintained at the proper operating level by preventing accumulation ofoil in the heat exchanger coils. In another aspect, therefrigerant-perfluoropolyether may also improve lubrication performanceof mineral oil and synthetic lubricant oils. In yet another aspect, therefrigerant-perfluoropolyether also improves heat transfer efficiencyand thus the energy efficiency of a refrigeration, air conditioning orheat transfer system. The refrigerant-perfluoropolyether has also beenshown to reduce friction and wear in boundary lubrication, which isexpected to result in longer compressor life. The advantages listedabove are not intended to be exhaustive.

Cooling capacity (also referred to as refrigeration capacity orcapacity) is a measure of the change in enthalpy of a refrigerant in anevaporator per pound of refrigerant circulated, i.e., the heat removedby the refrigerant in the evaporator per a given time. Therefore, thecapacity is a measure of the ability of a refrigerant or heat transfercomposition to produce cooling. The higher the capacity the greater thecooling that may be produced.

Energy efficiency (EER) is a term describing the efficiency of a coolingor heating system based upon the energy consumed in use.

Reference to “an effective amount of perfluoropolyether” in thisapplication means an amount of perfluoropolyether additive to providesufficient oil return to the compressor in order to maintain or improvelubrication or energy efficiency performance or both, wherein saidamount of perfluoropolyether is adjusted by one of ordinary skill to alevel appropriate to the individual refrigeration, air conditioning orheat transfer system (coil, compressor, etc.) and refrigerant or heattransfer fluid employed.

In some embodiments of this invention, the amount of perfluoropolyetheris less than 40% by weight relative to the refrigerant or heat transferfluid. In one embodiment, the amount of perfluoropolyether additive isless than about 20-30 wt. % relative to the refrigerant or heat transferfluid. In another embodiment, the perfluoropolyether additive is lessthan about 10 wt. % relative to the refrigerant or heat transfer fluid.In another embodiment, the perfluoropolyether additive is less thanabout 1 to about 2 wt. % relative to the refrigerant or heat transferfluid. In another embodiment, the perfluoropolyether additive is betweenabout 0.01 wt. % and 1.0 wt. % relative to the refrigerant or heattransfer fluid. In yet another embodiment, the perfluoropolyetheradditive is between about 0.03 and 0.80 wt. % relative to therefrigerant or heat transfer fluid.

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of a stabilizer, freeradical scavenger or antioxidant. Such other additives include but arenot limited to, nitromethane, hindered phenols, hydroxylamines, thiols,phosphites, or lactones. Single additives or combinations may be used.

Optionally, certain refrigeration or air-conditioning system additivesmay be added, as desired, to compositions of the present invention inorder to enhance performance and system stability. These additives areknown in the field of refrigeration and air-conditioning, and include,but are not limited to, anti wear agents, extreme pressure lubricants,corrosion and oxidation inhibitors, metal surface deactivators, freeradical scavengers, and foam control agents. In general, these additivesmay be present in the inventive compositions in small amounts relativeto the overall composition. Typically concentrations of from less thanabout 0.1 weight percent to as much as about 3 weight percent of eachadditive are used. These additives are selected on the basis of theindividual system requirements. These additives include members of thetriaryl phosphate family of EP (extreme pressure) lubricity additives,such as butylated triphenyl phosphates (BTPP), or other alkylatedtriaryl phosphate esters, e.g. Syn-0-Ad 8478 from Akzo Chemicals,tricresyl phosphates and related compounds. Additionally, the metaldialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate (or ZDDP),Lubrizol 1375 and other members of this family of chemicals may be usedin compositions of the present invention. Other antiwear additivesinclude natural product oils and asymmetrical polyhydroxyl lubricationadditives, such as Synergol TMS (International Lubricants). Similarly,stabilizers such as antioxidants, free radical scavengers, and waterscavengers may be employed. Compounds in this category can include, butare not limited to, butylated hydroxy toluene (BHT), epoxides, andmixtures thereof. Corrosion inhibitors include dodeceyl succinic acid(DDSA), amine phosphate (AP), oleoyl sarcosine, imidazone derivativesand substituted sulfphonates. Metal surface deactivators includeareoxalyl bis(benzylidene) hydrazide (CAS reg no. 6629-10-3),N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS reg no.32687-78-8),2,2,′-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (CASreg no. 70331-94-1), N,N′-(disalicyclidene)-1,2-diaminopropane (CAS regno. 94-91-7) and ethylenediaminetetra-acetic acid (CAS reg no. 60-00-4)and its salts, and mixtures thereof.

Additional additives include stabilizers comprising at least onecompound selected from the group consisting of hindered phenols,thiophosphates, butylated triphenylphosphorothionates, organophosphates, or phosphites, aryl alkyl ethers, terpenes, terpenoids,epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols,lactones, thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalic acid, diphenylterephthalic acid, ionic liquids, and mixtures thereof. Representativestabilizer compounds include but are not limited to tocopherol;hydroquinone; t-butyl hydroquinone; monothiophosphates;dithiophosphates, such as Irgalube® 63 (Ciba Specialty Chemicals, Basel,Switzerland); dialkylthiophosphate esters, such as Irgalube® 353 (Ciba)and Irgalube® 350 (Ciba); butylated triphenylphosphorothionates, such asIrgalube® 232 (Ciba); amine phosphates, such as Irgalube® 349 (Ciba);hindered phosphites, such as Irgafos 168(Tris-(di-tert-butylphenyl)phosphite—Ciba), Irgafos OPH (Di-n-octylphosphite—Ciba), and Irgafos DDPP (Iso-decyl diphenyl phosphite—Ciba);anisole; 1,4-dimethoxybenzene; 1,4-diethoxybenzene;1,3,5-trimethoxybenzene; d-limonene; retinal; pinene; menthol; VitaminA; terpinene; dipentene; lycopene; beta carotene; bornane; 1,2-propyleneoxide; 1,2-butylene oxide; n-butyl glycidyl ether;trifluoromethyloxirane; 1,1-bis(trifluoromethyl)oxirane;3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd);3-ethyl-3-((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co.,Ltd); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, such as OXT-212(Toagosei Co., Ltd); ascorbic acid; methanethiol(methyl mercaptan);ethanethiol (ethyl mercaptan); Coenzyme A; dimercaptosuccinic acid(DMSA); grapefruit mercaptan((R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol)); cysteine((R)-2-amino-3-sulfanyl-propanoic acid); lipoamide(1,2-dithiolane-3-pentanamide); 5,7-bis(1,1-dimethylethyl)-3-[2,3(or3,4)-dimethylphenyl]-2(3H)-benzofuranone, such as Irganox® HP-136(Ciba); benzyl phenyl sulfide; diphenyl sulfide; diisopropylamine;dioctadecyl 3,3′-thiodipropionate, such as Irganox® PS 802 (Ciba);didodecyl 3,3′-thiopropionate, such as Irganox® PS 800 (Ciba);di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, such as Tinuvin® 770(Ciba); poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidylsuccinate, such as Tinuvin® 622LD (Ciba); methyl bis tallow amine; bistallow amine; phenol-alpha-naphthylamine; bis(dimethylamino)methylsilane(DMAMS); tris(trimethylsilyl)silane (TTMSS); vinyltriethoxysilane;vinyltrimethoxysilane; 2,5-difluorobenzophenone;2′,5′-dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone;benzyl phenyl sulfide; diphenyl sulfide; dibenzyl sulfide; ionicliquids; and others as disclosed in International Patent Application No.PCT/US07/07477, filed Mar. 26, 2007.

Ionic liquid stabilizers comprise at least one ionic liquids. Ionicliquids are organic salts that are liquid at room temperature(approximately 25° C.). In another embodiment, ionic liquid stabilizerscomprise salts containing cations selected from the group consisting ofpyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium,pyrazolium, thiazolium, oxazolium and triazolium; and anions selectedfrom the group consisting of [BF₄]—, [PF₆]—, [SbF₆]—, [CF₃SO₃]—,[HCF₂CF₂SO₃]—, [CF₃HFCCF₂SO₃]—, [HCCIFCF₂SO₃]—, [(CF₃SO₂)₂N]—,[(CF₃CF₂SO₂)₂N]—, [(CF₃SO₂)₃C]—, [CF₃CO₂]—, and F—. Representative ionicliquid stabilizers include emim BF₄ (1-ethyl-3-methylimidazoliumtetrafluoroborate); bmim BF₄ (1-butyl-3-methylimidazolium tetraborate);emim PF₆ (1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF₆(1-butyl-3-methylimidazolium hexafluorophosphate), all of which areavailable from Fluka (Sigma-Aldrich).

Lubricants used in this invention include natural and syntheticlubricant oils. A preferred example of natural lubricant oil is mineraloil. Other, synthetic lubricant oils including alkylbenzene, polyolester, polyalkylene glycols, polyvinyl ethers, carbonates andpolyalphaolefin may also be used. In one aspect of the invention,perfluoropolyether is used together with mineral oil.

In another aspect of the invention, perfluoropolyether is used togetherwith synthetic lubricant oils.

In some embodiments of this invention, the amount of perfluoropolyetheris less than 50% by weight relative to the mineral oil. In oneembodiment, the amount of perfluoropolyether is less than 20% by weightrelative to the mineral oil. In another embodiment, the amount ofperfluoropolyether is less than 5% by weight relative to the mineraloil. In yet another embodiment, the amount of perfluoropolyether is lessthan 3 wt. % relative to the mineral oil.

In one embodiment of this invention, the refrigeration or heat transferfluid composition comprises a mineral oil, perfluoropolyether, and arefrigeration or heat transfer fluid selected from the group consistingof R-407C, R-422A, R-417A, R-404A, R-410A, R-507A, R-508A, R-422A,R-417A, and HFC-134a.

In another embodiment of this invention, the refrigeration or heattransfer fluid composition comprises a perfluoropolyether and anunsaturated fluorocarbon such as 1,2,3,3,3-pentafluoro-1-propene,1,1,3,3,3-pentafluoro-1-propene, 1,1,2,3,3-pentafluoro-1-propene,1,2,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene,1,3,3,3-tetrafluoro-1-propene, 1,1,2,3-tetrafluoro-1-propene,1,1,3,3-tetrafluoro-1-propene, 1,2,3,3-tetrafluoro-1-propene,1,1,1,2,3,4,4,4-octafluoro-2-butene, 1,1,1,2,4,4,4-heptafluoro-2-butene,1,1,1,4,4,4-hexafluoro-2-butene, or mixtures thereof.

The present invention further relates to a method of using therefrigeration or heat transfer fluid compositions of the presentinvention for producing refrigeration or heating, wherein the methodcomprises producing refrigeration by evaporating said composition in thevicinity of a body to be cooled and thereafter condensing saidcomposition; or producing heat by condensing said composition in thevicinity of the body to be heated and thereafter evaporating saidcomposition.

The present invention further relates to a process for transfer of heatfrom a heat source to a heat sink wherein the compositions of thepresent invention serve as heat transfer fluids. Said process for heattransfer comprises transferring the compositions of the presentinvention from a heat source to a heat sink.

Heat transfer fluids are utilized to transfer, move or remove heat fromone space, location, object or body to a different space, location,object or body by radiation, conduction, or convection. A heat transferfluid may function as a secondary coolant by providing means of transferfor cooling (or heating) from a remote refrigeration (or heating)system. In some systems, the heat transfer fluid may remain in aconstant state throughout the transfer process (i.e., not evaporate orcondense). Alternatively, evaporative cooling processes may utilize heattransfer fluids as well.

A heat source may be defined as any space, location, object or body fromwhich it is desirable to transfer, move or remove heat. Examples of heatsources may be spaces (open or enclosed) requiring refrigeration orcooling, such as refrigerator or freezer cases in a supermarket,building spaces requiring air-conditioning, or the passenger compartmentof an automobile requiring air-conditioning. A heat sink may be definedas any space, location, object or body capable of absorbing heat. Avapor compression refrigeration system is one example of such a heatsink.

The present invention further relates to a method of using theperfluoropolyether to maintain or improve the oil return, lubrication,or energy efficiency of the refrigeration, air conditioning and heattransfer system. The method comprises adding an effective amount ofperfluoropolyether into the refrigeration or air-conditioning apparatus.This may be done by mixing the perfluoropolyether with the refrigerantor heat transfer fluid compositions of this invention and thenintroducing the combination into the apparatus. Alternatively, this maybe done by directly introducing perfluoropolyether into refrigeration orair-conditioning apparatus containing refrigerant and/or heat transferfluid to combine in situ with the refrigerant. The resulting compositionmay be used in the refrigeration or air-conditioning apparatus.

The present invention further relates to a method of using theperfluoropolyether to maintain or improve the oil return, lubrication,or energy efficiency by replacing the existing refrigerants or heattransfer fluids without changing the existing lubricants in therefrigeration or air-conditioning apparatus. The method comprisesremoving the existing refrigerant or heat transfer fluid from therefrigeration or air-conditioning apparatus without flushing out theexisting lubricant. Said refrigeration or air-conditioning apparatus isthen filled with a pre-mixed composition comprising perfluoropolyetherand the refrigerant or heat transfer fluid compositions of thisinvention.

The compositions of the present invention may be used in stationaryrefrigeration, air-conditioning, and heat pumps or mobileair-conditioning and refrigeration systems. Stationary air-conditioningand heat pump applications include window, ductless, ducted, packagedterminal, chillers and light commercial and commercial air-conditioningsystems, including packaged rooftop. Refrigeration applications includedomestic or home refrigerators and freezers, ice machines,self-contained coolers and freezers, walk-in coolers and freezers andsupermarket systems, and transport refrigeration systems.

Mobile refrigeration or mobile air-conditioning systems refer to anyrefrigeration or air-conditioning system incorporated into atransportation unit for the road, rail, sea or air. In addition,apparatus, which are meant to provide refrigeration or air-conditioningfor a system independent of any moving carrier, known as “intermodal”systems, are included in the present invention. Such intermodal systemsinclude “containers” (combined sea/land transport) as well as “swapbodies” (combined road and rail transport). The present invention isparticularly useful for road transport refrigerating or air-conditioningapparatus, such as automobile air-conditioning apparatus or refrigeratedroad transport equipment.

In one embodiment of this invention, the compositions of the presentinvention (for example, a composition comprising a mineral oil,perfluoropolyether, and a refrigeration or heat transfer fluid selectedfrom the group consisting of R-407C, R-422A, R-417A, R-404A, R-410A,R-507A, R-508A, and HFC-134a) can be used in a heat pump with“internally enhanced heat transfer surfaces”, i.e. heat pumps with finegrooves cut in a spiral or cross hatch pattern on the inside surface ofthe tube.

As demonstrated by the Examples below, the addition ofperfluoropolyether into the refrigerant increased the oil return orenergy efficiency or cooling capacity of the refrigeration or heattransfer system. In one embodiment of the invention, Krytox® 157FSH issufficiently miscible with HFC refrigerants including R-134a, R-125, andR-32 such that the Krytox® can be blended with the refrigerant blend andcharged to the refrigeration or air conditioning apparatus as ahomogeneous liquid. These examples also demonstrate that the use of PFPEadditives is beneficial in retrofits of existing systems to systemsutilizing new refrigerant or heat transfer fluids that use POE, mineraloil or alkylbenzene lubricants.

EXAMPLES Example 1

Miscibility of 1,1,1,2-tetrafluoroethane (HFC-134a) with representativemembers of the family of Krytox® perfluoropolyethers, including Krytox®1531, Krytox® GPL-103, Krytox® 157 FSM, and Krytox® 143AZ wasdemonstrated by adding 1.0 gram of the PFPE to individual glass highpressure chemical bottles. Each bottle was fitted with a sealed additionvalve which could be coupled to a pressure burette from which liquefiedrefrigerant could be added to the bottle. This was followed by addingaliquots of HFC-134a, first one gram, then about 2 grams per additionalaliquot, to yield higher and higher mixing ratios of the HFC, up to amaximum of 99 grams of HFC-134a in each bottle. After each aliquot wasadded the bottle and its contents were swirled to mix, then observed forindication of sign of insolubility, such as the formation of haze,cloudiness, or a second liquid layer. In every case the contents of thebottle remained as one single clear liquid phase at all compositions.This showed that at room temperature, each of the perfluoropolyetherswas fully soluble in the HFC-134a over a range of mixing ratios rangingfrom about 50% to about 1% by weight in HFC-134a.

Example 2

Baseline Refrigeration Oil Circulation tests were run in a commercialtype reach-in refrigerator manufactured by Zero Zone, Inc. of 110 NorthOak Ridge Drive, North Prairie, Wis., Model #2SMCP26. The Copelandcompressor in the unit (Copeland Model # ARE59C3CAA-901) was fitted withan oil level indicating tube (sight glass) which showed the level oflubricating oil in the crank case of the compressor. The refrigeratorwas installed in a constant temperature room in which the roomtemperature was regulated at a constant 90 degrees Fahrenheit. In a baseline run with R-22 (chlorodifluoromethane) and Suniso 4GS mineral oil,the oil level in the compressor remained constant after a small initialdecrease at startup, indicating that the oil which left the compressorwith the refrigerant circulated through the system and came back withthe suction gas, and thereby a constant, steady state level of oil wasmaintained within the compressor crank case. This constant oil levelassured adequate lubrication and sealing of compressor internal parts,while some small amount of oil which left the compressor with thecompressed refrigerant gas circulated through the condenser, the thermalexpansion valve, and the evaporator coil before returning to thecompressor with the suction gas. This was indicative of normal operationof the cooling loop. Through out the duration of this 24-hour test therefrigerator maintained a constant temperature of 37 degrees Fahrenheitin the cooling zone.

Example 3 (Comparative)

The same kind of oil circulation test as described in Example 2 abovewas run, only this time the R-22 (chlorodifluoromethane) refrigerant hadbeen removed and replaced with Refrigerant R-422A, a blend of HFC-125(85.1 wt. %), HFC-134a (11.5 wt. %), and isobutane (3.4 wt. %). Whenthis refrigerant ran in the Zero Zone refrigerator, the level of oil inthe crankcase steadily decreased with time as the system operated tomaintain a standard temperature of 37 degrees Fahrenheit in therefrigerated case. In a period of six hours, the oil level had droppedto the minimum allowable level within the crankcase, and the run had tobe terminated to prevent compressor damage. This showed that with thiscombination of refrigerant and lubricant, the lubricant slowly gotpumped out of the compressor and did not return.

Example 4 (Comparative)

After the oil return test described in Example 3 above was completed,the refrigerant system was flushed with R-22 (chlorodifluoromethane) toremove the excess oil from the heat exchangers, and normal base lineoperation was demonstrated with R-22. After the baseline re-check, onceagain the refrigerant R-22 was removed and replaced again with a freshcharge of R-422A and Suniso 4GS mineral oil as above, to which a smallamount, equivalent to about 0.1% by weight, relative to the refrigerantcharge, of the Krytox® Perfluoropolyether GPL-101 was added. Therefrigerator was re-started and allowed to run as described in Example 3above. Surprisingly, the system ran with adequate oil showing in thesight glass for 18 hours, three times longer than in Example 3, whichhad no added perfluoropolyether.

Example 5 (Comparative)

After the oil return test described in Example 4 above was completed,the refrigerant system was flushed with R-22 to remove the excess oiland any remaining perfluoropolyether from the heat exchangers, andnormal base line operation was demonstrated with R-22 and Suniso 4GSmineral oil. After the baseline re-check, once again the refrigerantR-22 was removed and replaced again with a fresh charge of R-422A andSuniso 4GS mineral oil as above, to which a small amount, equivalent toabout 0.1% by weight, relative to the refrigerant charge, of the Krytox®Perfluoropolyether 157FSL was added. The refrigerator was re-started andallowed to run as described in Example 3 above. Surprisingly, the systemran with adequate oil showing in the sight glass for 24 hours, fourtimes longer than in Example 3, which had no added perfluoropolyether.There was still an adequate oil level showing in the sight glass whenthe run was terminated.

Example 6 (Comparative)

The ZeroZone commercial reach in refrigerator described above wasre-fitted with a thermal expansion valve to allow it to operate with theHFC refrigerant R-404A (a blend of 44 wt. % of HFC-125, 52 wt. ofHFC-143a and 4 wt. % of HFC-134a) and Suniso 4GS mineral oil. Thisrefrigerator was operated at an internal box temperature of 38 degreesFahrenheit while energy consumption was monitored. As before, the testwas conducted with the refrigerator in a constant temperature room thatwas controlled at a constant temperature of 90 degrees Fahrenheit.During a three-hour test period the power consumption of therefrigerator was measured to be at a rate of 22.65 Kilowatt hours perday.

Example 7 (Comparative)

The Test set up described in example 6 above was modified by removingthe refrigerant charge, and re-charging with a mixture of refrigerantR-404A and Suniso 4GS mineral oil which contained 0.2% by weight,relative to the refrigerant charge, of Krytox® 157 FSH. The test chamberwas stabilized again at 90 degrees, and the refrigerator was allowed tooperate. Over a three-hour period the internal box temperature wasmaintained at 37.6 degrees Fahrenheit. The average power use by therefrigerator during this test period was measured to be at a rate of21.83 Kilowatt hours per day. This was 3.6% less power usage than wasmeasured in Example 6, when no Krytox® was in the refrigerant.

Example 8

Boundary Layer Lubrication tests were run using a FALEX Pin on vee-blocktest geometry, according to test protocol based on the ASTM 2670-95 Loadto Failure test method. In this test, a rotating steel pin was squeezedbetween two standard blocks of aluminum metal. The aluminum blocks weremade with vee shaped notches in them, and they were mounted in a bracketsuch that the vee notches contacted the steel pin. The pin and blockassembly was immersed in a pan of lubricant and a motor coupled througha torque meter rotated the pin. The blocks were adjusted to lightlycontact the surface of the rotating pin at a low load of 250-poundspressure for an initial run-in period of five minutes. The force loadapplied to the blocks was then increased slowly at a steady rate of 200more pounds each minute by a mechanical tightener that squeezed therotating pin between the two vee blocks. The load was increased to somepredetermined limit, or until a mechanical failure of one of the testpieces occurred. With pure Suniso 4GS mineral oil, the test failedwithin the first minute, while the mechanical load on the pin and blockassembly was only 250 lb. Surprisingly, when this test was repeated witha mixture of 0.5% by weight of Krytox® 157 FSL dispersed in the Suniso4GS mineral oil, the test continued to run for 9 minutes, during whichtime the mechanical load had increased to a level of 2100 pounds. Bythis time the mechanical parts had not failed, but the level of smokebeing generated became excessive, so the test was terminated. Thisshowed that the presence of small amount of Krytox® 157 FSL dispersed inthe mineral oil increased the load carrying ability of the mineral oilat boundary lubrication conditions by more than 800%.

Example 9

A split system Carrier heat pump was used to evaluate refrigerant andlubricant performance in air conditioning and heating modes. The systemconsisted of a condensing unit, Model 38YXA030, and an evaporator Unit,Model FX4ANF030, and was rated at a nominal cooling capacity of 2½ tonsof cooling with R-410A. The system was operated inside of a dual chamberpsychrometric chamber, with one chamber regulated at outdoor conditionsper standard ARI 210/240 Cooling A test conditions, and the otherchamber regulated at Cooling A indoor test conditions. This unit wasalso modified so that the compressor could be changed from the standardR-410A rated compressor to a compressor sized for operation with R-407C.In the tests cited in Table 4 below, runs 1, 2, and 3 were made usingthe R-410A compressor. Runs 4, 5, 6, and 7 were made with the R-407Ccompressor.

The copper tubing in the evaporator and condenser coils of this airconditioning system came from the factory with a feature called“internally enhanced heat transfer surfaces”, a feature which isgenerally known and used throughout the industry. This feature includesfine grooves cut in a spiral or cross hatch pattern on the insidesurface of the tube. These grooves cause disruption of the laminar flowlayers near the tube surface. The result of this disruption is believedto be improved heat transfer from the evaporating refrigerant within thecopper tubes to the tubes themselves and the attached fins that comprisethe evaporator unit. Heat transfer to the air flowing through the finsof the evaporator is believed to be thereby improved, with the creationof a more energy efficient air conditioning or heating process. Again,the use of internally enhanced tube surfaces is well known and widelyapplied within the air conditioning and heat pump industries. Most highefficiency systems employ enhanced surface tubing in evaporators andcondensers.

It has been observed that when a lubricant that is not miscible with therefrigerant is used in such an enhanced system, that the performanceimprovement normally imparted by the enhanced tube surface is lost. Itis believed that the non-miscible lubricant is drawn into the finegrooves by capillary action, effectively creating a smoother surface.This smoother surface is believed to cause at least a partial return tothe less efficient laminar flow of the refrigerant within the tube.Further, the layer of oil on the tube surface is believed to reduces theability of the copper tube to allow heat transfer, further reducingoperating efficiency. As shown in Table 4, the addition of a smallamount of PFPE to the refrigerant in our heat pump system willsubstantially reduce the deficit in performance which results from theuse of a non miscible lubricant, such as mineral oil, with an HFCrefrigerant such as R-410A or R-407C. This ability of the heat pump tooperate with HFC refrigerant and non miscible mineral oil with excellentefficiency is shown by the data in Table 4 below.

TABLE 4 Impact of adding PFPE to Carrier Heat Pump Ca- EER pacity DeltaDelta Run vs. Capacity vs. # Refrigerant Lubricant Additive EER POEkBTU/h POE 1 410A 32-3MA none 12.8 28.6 2 410A 3GS none 11.1 87.2 25.087.4 3 410A 3GS 0.2% 12.5 97.9 28.1 98.5 157 FSL 4 R-407C RL32H none11.2 27.8 5 R-407C 3GS none 10.8 96.7 26.6 95.5 6 R-407C 3GS 1% 11.098.3 27.6 99.0 157 FSL 7 R-407C RL32H 1% 11.3 101.0 27.6 99.2 157 FSLThese POE lubricants are miscible with the refrigerants used in theexample. The lubricant 3GS is a commercial naphthenic mineral oilavailable from Sonneborn, Inc. The mineral oil lubricant is not misciblewith HFC refrigerants.

In Table 4, note that when the non miscible lubricant Suniso 3GS, amineral oil, is used with HFC refrigerant R-410A, (Run #2) the EER isreduced by 12.8%, and the capacity reduced by 12.6%, versus Run #1 withPOE lubricant. However, when a small amount of the PFPE Krytox® 157 FSLis added to the refrigerant (Run #3) that the EER is restored to withinabout 2.1% of that achieved with POE, and the capacity is restored towithin about 1.5% of that achieved with POE. The deficits caused by theuse of the non-miscible mineral oil are almost completely eliminated bythe use of PFPE.

Further note in Table 4 that with HFC refrigerant R-407C, when mineraloil is used the efficiency and capacity are reduced by about 3.3% and4.5%, respectively versus POE. (Runs 4 and 5). In Run #6 it is seen thatthe addition of 1% Krytox® 157 FSL increases the EER and capacity towithin 1.7% and 1.0%, respectively, of the values obtained with the POElubricant. Again, the deficits caused by using non-miscible lubricantare largely eliminated by the use of the PFPE.

Finally note that when Krytox 157 FSL was added to the R-407C and POEsystem (Run 6) that the EER was improved to be 1% better than thatobtained in Run 4 with no PFPE, and the capacity was within 1% of Run 4,the POE baseline case.

Example 10

In a similar manner to Example 9, a split system Carrier Heat Pump wasused to measure performance of several compositions as disclosed hereinas compared to compositions with no perfluoropolyether additive. Theunit was a residential-type heat pump unit manufactured by Carrier Corp.(Model #38YXA030) with a Carrier Air Handler (Model # FX4ANF030). TheCopeland Scroll compressor (Model # ZR28K3-PFV) was fitted with an oillevel indicating tube (sight glass) which showed the level oflubricating oil in the crank case of the compressor.

The outdoor (Model #38YXA030 from above) and indoor (Model# FX4ANF030)units were installed in temperature and humidity controlledenvironmental chambers and tested per ARI Standard 210/240. Per the “A”Cooling Steady State Test in the standard, the outdoor room temperaturewas controlled to 95° F. dry bulb and 75° F. wet bulb temperature andthe indoor unit was controlled to 80° F. dry bulb and 67° F. wet bulbtemperature. The amount of superheat was controlled at a constant 20degrees F. The charge size for the lubricant was a constant 1200 mL asrecommended on the compressor nameplate. Data was collected for 2 hoursfor each test at steady state conditions and oil level in the sightglass was monitored at regular intervals.

The refrigerant composition tested was a mixture of 62.3 weight percentHFC-1225ye, 24 weight percent HFC-32, and 13.7 weight percent HFC-125 ascombined with either Suniso 3GS mineral oil or RL32-3MAF POE lubricantsand Krytox® GPL-104 additive. The results are listed in Table 5.

TABLE 5 EER, Capacity, Run % of Capacity % of # Lubricant Additive EERPOE (KBtu/hr) POE 1 RL32-3MAF none 10.4 100.0% 25.0 100.0% 2 RL32-3MAF0.2% 10.6 102.1% 24.7  99.0% GPL-104 3 3GS none 10.1  97.1% 23.9  95.6%4 3GS 0.2% 10.4  99.9% 24.9  99.5% GPL-104

In Table 5, note that when the non-miscible mineral oil Suniso 3GSlubricant is used with the HFC refrigerant (Run#3), the energyefficiency (EER) is reduced 2.9% and the capacity is reduced 4.4% whencompared to the miscible POE RL32-3MAF lubricant (Run#1). However, whena small amount of Krytox® GPL-104 PFPE is added to the 3GS system(Run#4), the energy efficiency is restored to within 0.1% and thecapacity is restored to within 0.5% of the values for the POE. Thedeficits caused by the use of the non-miscible mineral oil lubricant arealmost completely eliminated by the use of the PFPE additive.

Further, addition of the PFPE to the POE system also shows animprovement in energy efficiency of 2.1% with minimal reduction incapacity.

The many features and advantages of the present invention are apparentfrom the detailed description above, and thus it is intended that theappended claims cover all such features and advantages which fall withinthe spirit and scope of the invention. In short, the foregoingdescription is illustrative of the invention, and is not intended toimply limitations thereupon. For example, where a numerical range islisted above, it is intended that the range include and herein expresslydisclose all numbers between the upper and lower limits, such that therange of from about 1 to about 10 would include also the numbers 2, 3,4, 5, 6, 7, 8 and 9. Numerous modifications and variations will readilyoccur to those skilled in the art, and it is not desired to limit theinvention to the exact composition, method and uses described above, andaccordingly, all suitable modifications and equivalents may be resortedto and fall within the scope of the invention described in the claims.

What is claimed is:
 1. A method of producing refrigeration, said methodcomprising evaporating a composition in the vicinity of a body to becooled and thereafter condensing said composition; wherein saidcomposition consists of: a. a refrigerant or heat transfer fluidconsisting of 2,3,3,3-tetrafluoro-1-propene (CH₂═CFCF₃) or1,3,3,3-tetrafluoro-1-propene (CHF═CHCF₃); and b. at least oneperfluoropolyether; and optionally c. a lubricant oil which is mineraloil or synthetic oil selected from the group consisting of alkylbenzene,polyol ester, polyalkylene glycols, polyvinyl ethers, carbonates,polyalphaolefin and combinations thereof; wherein saidperfluoropolyether has two end groups; wherein each of the two endgroups of the perfluoropolyether, independently, is either anunfunctionalized, branched or straight chain perfluoroalkyl radical, ora functionalized group selected from the group consisting of esters,hydroxyls, amines, amides, cyanos, carboxylic acids and sulfonic acids;and wherein said evaporating and said condensing is in a mobileair-conditioning system.
 2. The method of claim 1, wherein the amount ofperfluoropolyether in said composition is less than about 40% by weightrelative to said refrigerant or heat transfer fluid.
 3. The method ofclaim 1, wherein at least one of the end groups of saidperfluoropolyether is carboxylic acid.
 4. The method of claim 1, whereinat least one of the end groups of said perfluoropolyether is sulfonicacid.
 5. The method of claim 1, wherein the mobile air-conditioningsystem is an automobile air-conditioning apparatus.